Polymeric surfactants based upon alkyl polyglycosides and sorbitan esters

ABSTRACT

The present invention relates to a series of polyglycoside derivatives that are (a) polymeric (that is cross linked with hydroxypropyl linkages) and (b) contain additional functional groups including alkoxy, sulfate, sulfonate, quaternary and phosphate groups, and (c) sorbitan esters to increase oil solubility and provide outstanding emulsifiers.

RELATED APPLICATIONS

This application claims priority to and benefit of U.S. ProvisionalApplication No. 61/276,301 filed Sep. 11, 2009, the disclosure of whichis incorporated herein for all purposes.

FIELD OF THE INVENTION

The present invention relates to a series of polyglycoside derivativesthat are (a) polymeric (that is cross linked with hydroxypropyllinkages) and (b) contain additional functional groups including alkoxy,sulfate, sulfonate, quaternary and phosphate groups, and (c) sorbitanesters to increase oil solubility and provide outstanding emulsifiers.

Commercial alkyl polyglycosides generally have a low degree ofpolymerization of polysaccharide, in the molecule. This results in amolecule that is of limited water solubility, and essentially noemulsification properties. The present invention is aimed atfunctionalizing the hydrophobic alkyl polyglycoside, making them evenmore hydrophobic and surprisingly emulsifiers. The raw materials uponwhich these materials are based have been called “alkyl glycosides,alkyl glycosides, alkyl polyglycosides or alkyl polyglycosides” by manydifferent authors. All refer to the same molecules.

BACKGROUND

Alkyl polyglycosides have been known for many years, having been firstsynthesized in the early 1900 by Emile Fischer. Despite this, theproducts were of little commercial interest until much later.

U.S. Pat. No. 4,393,203 issued Jul. 12, 1983 to Mao et al, incorporatedherein by reference, disclose that long chain fatty alcohols can beremoved from alkyl polysaccharide products in thin film evaporators toachieve fatty alcohol levels of less than about 2% without excessivediscoloration of the alkyl polysaccharide. This allowed for a morecosmetically acceptable product to be developed that is more surfaceactive. The presence of the free fatty alcohol in the mixture, allowsfor a more water-soluble product, by removing the water insolublealcohol.

One of the most significant patents is U.S. Pat. No. 5,003,057 issuedMar. 26, 1991 to McCurry et al incorporated herein by reference,provides for a process for preparing glycosides from a source ofsaccharide moiety and an alcohol in the presence of a hydrophobic acidcatalyst is provided. An example of such a catalyst isdinonylnaphthalenemonosulfonic acid. The use of such catalysts providesa number of process advantages, which includes the reduced production ofpolar by-products. Preferred glycosides produced by the process arehigher alkyl glycosides useful as surfactants.

U.S. Pat. No. 3,598,865 (Lew) discloses the production of higher alkyl(C⁻⁸-C₂₅) glycosides from a monosaccharide or source thereof and ahigher monohydric alcohol in the presence of a latent solvent (loweralcohols) and an acid catalyst selected from the group consisting ofsulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid,toluenesulfonic acid, and boron trifluoride.

U.S. Pat. No. 3,219,656 (Boettner) discloses a process for producing ahigher alkyl glycoside by reacting glucose with methanol in the presenceof a macroreticular-structured sulfonic acid resin, anhydrous and in theacid form, to produce methyl glycoside which is reacted withoutisolation with butanol to form butyl glycoside and which in turn isreacted with a higher alcohol to form a surface active higher alkylglycoside.

U.S. Pat. No. 3,839,319 (Mansfield) discloses a process for producingalkyl glycosides by direct, acid catalyzed reaction of a higher alcoholand a saccharide. The acid catalysts are mineral acids such ashydrochloric and sulfuric, and sulfonic acid exchange resins

The compounds known before the current invention have been primarilyused in industrial applications like detergents for dish wash. This isdue in part to inherent drying that occurs when these materials areapplied to the skin. Many people, one of which is Cognis, haveintroduced blends of alkyl polyglycosides and traditional surfactants toovercome these limitations. The blending of other alternativesurfactants, while demonstrating a long felt need for improvement in theperformance of the product, does not address underlying difficulties inthe molecule.

U.S. Pat. No. 4,297,290 to Stockberger issued Oct. 27, 1981 teaches thatsorbitan fatty acid esters can be prepared by forming anhydro sorbitol(a mixture of sorbitans, isosorbide, and unreacted sorbitol) byacid-catalyzed anhydrization, then reacting the resulting anhydrosorbitol with a fatty acid in the presence of a base at a temperaturenot exceeding about 215° C. Use of temperatures not over 215° C. resultsin products having substantially less color than those obtained athigher temperatures. It is these hydrophobic materials that are the rawmaterial for synthesis of the emulsifiers of the present invention.

U.S. Pat. No. 7,556,653 to LaVay et al issued Jul. 7, 2009 entitledPolymeric silicone alkoxyglyceryl softeners teaches a class ofpolyesters that are lightly crosslinked polyesters made by reactingalkoxy glyceryl units (linked by the reaction of their hydroxyl groups)to the carboxyl group of dimer acid. As will become clear, lightlycrosslinked as used herein relates to reactions in which there is anexcess of hydroxyl groups on a molar basis to carboxylic groups on thedimer acid. The polymers and a contribute softness, lubricity andantistatic properties when applied to hair, skin, textile fiber andpaper. This patent teaches that dimer acid can be used to crosslinkpolysorbates to make conditioners. This patent provides conditioners notemulsifiers, and lacks the critical element of alkyl polyglycoside andcrosslinker.

U.S. Pat. No. 7,507,399 issued Mar. 24, 2009 to O'Lenick entitledFunctionalized polymeric surfactants based upon alkyl polyglycosidesteaches a series of multifunctional polyglycosides derivatives that aremade by the polymerized by the reaction of 1,3 dichloro isopropanl andpolyglycosides, together with a functionalizing agent that contains asulfate, sulfonate, quaternary nitrogen, or a phosphate group. Thispatent lacks the critical element of the sorbitan ester to make anemulsifier.

All patents referenced above are incorporated herein by reference. Noneof the patents referenced above either alone or combination teach orsuggest the making of the compounds of the present invention, namelycombining the sorbitan ester with the alkylpolyglycoside and thecrosslinker.

THE INVENTION

The present invention relates to the finding that the reaction of alkylpolyglycosides, sorbitan esters and the proper additional reagentresults in molecules that is an excellent emulsifier. It is mostinteresting that the maximum amount of glycoside units per alkyl groupthat can be added using known technology is 1.5. This means that theproduct is a mixture of mono and di functional product. This product hasthe remaining fatty alcohol stripped off in an evaporative process. Theresulting product is about 70% by weight of a product of a d.p. of 1,about 21% by weight of a product of a d.p. of 2, about 7% by weight of aproduct having a d.p. of 3, and about 2% by weight of a product that hasa d.p. of 4.

We have surprisingly learned that taking the alkyl polyglycosidesproduced in the commercial process, with its inherent properties to makethem emulsifiers even when cross linked polymers, and include functionalgroups, including alkoxy, sulfate, sulfonate, quaternary and phosphategroups results in a series of products that are much more usable in manyapplications.

SUMMARY OF THE INVENTION

Alkyl polyglycosides are complex products made by the reaction ofglucose and fatty alcohol. In dealing with the chemistry one talks aboutdegree of polymerization (the so called “d.p.”). In the case oftraditional alkyl polyglycosides the d.p. is around 1.4. This means thaton average there is 1.4 units of glucose for each alkyl group. The factof the matter is that the resulting material is a mixture having anaverage of 1.4.

The specific structure of the product is hard to ascertain completelysince many positional isomers are possible, but two examples ofstructures are as follows;

It should be clear that if there is a 50/50 mixture of the d.p. 1 andd.p. 2 product, the resulting analytical data will show that on averagethere is a d.p. of 1.5. Saying that a molecule has a d.p. of 1.5 doesnot mean that each molecule has 1.5 glucose units on it.

One key aspects of the present invention relates to the heretoforeunappreciated fact that by polymerizing the alkyl polyglycosidestogether with specific hydrophobic sorbitan esters using the processspecified in U.S. Pat. No. 7,507,399 issued Mar. 24, 2009 to O'Lenickentitled Functionalized polymeric surfactants based upon alkylpolyglycosides provides a route to outstanding emulsifiers free ofethylene and propylene oxide.

Another key unappreciated fact in making the compounds of the presentinvention is the selection of the proper reagents to make the desiredproduct. Specifically, the reaction of the alkyl polyglycoside togetherwith the sorbitan ester with a certain family of epoxy compounds andrelated materials occurs under mild aqueous conditions and results in anoutstanding emulsifier derived from natural ingredients.

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention are prepared by reacting themixtures conform to the following structures:

wherein;

R is alkyl having 8 to 22 carbon atoms;

and

wherein;

R is alkyl having 8 to 22 carbon atoms;

(c) a sorbitan ester conforming to the following structure:

R¹ is alkyl having from 7 to 21 carbon atoms;with a polymerizing agent conforming to the following structure

-   -   Cl—CH₂CH(OH)CH₂Cl        and        optionally a functionalizing agent selected from the group        consisting of

Cl—CH₂—CH(OH)—SO₃M;Cl—CH₂—CH(OH)CH₂—SO₄M;Cl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂;and mixtures thereof;wherein:R¹ is CH₃—(CH₂)n is an integer ranging from 6 to 36;M is needed for charge balance and is selected from the group consistingof

-   -   H, Na, K, or NH₄.

It will become clear that the compositions of the present invention needto be claimed as product by process, since they are the reaction productof two multi-hydroxyl product (alkyl polyglycosides and sorbitan esters)and a di-chloro intermediate. Since there is not a great deal of groupspecificity in the reaction of the various hydroxyl groups, cross linkedpolymers result. The degree of cross linking depends upon the ratio of1,3 dichloro isopropanol to hydroxyl groups chosen. The functionalizingagent likewise reacts with hydroxyl groups, providing a multifunctionalpolymer.

By considering the reaction in steps, it will make the reaction pathwayclearer.

The 1,3 dichloro-isopropanol reacts with the first hydroxyl group givingan intermediate:

The above reaction shows only one of the possible reacted hydroxylgroups on one hydroxyl rich compound, the alkyl polyglycoside. There isan equal potential for reaction of the other hydroxyl groups on thealkyl polyglycoside and the sorbitan ester as well, and in fact there ifformed a random polymer of sorbitan ester units and alkyl poylglycosideunits having a hydroxy propyl linkage. Subsequently, another hydroxylgroup reacts to give:

Functionalization

The optional functionalization group is added to one of the additionalhydroxyl groups for example:

whereinR² is —CH₂—CH(OH)—CH₂—SO₃Na.

As the reaction continues more and more hydroxyl groups react, comingfrom the alkyl poylglycoside and the sorbitan ester with either thepolymerizing agent or the functionalizing agent. The structure iscomplicated not only by the fact that many hydroxyl groups, on APG(alkyl polyglycoside) or on sorbitan ester can react with the differenttypes of agent, but also by the fact that commercial polyglycosides aremixtures having an average dp of 1.5. The resulting products arehydroxypropyl cross linked polymers having branching present. This isthe reason for claiming the products in a product by process format.

Another aspect of the present invention is a process for conditioninghair and skin which comprises contacting the hair and skin with aneffective conditioning concentration of a composition prepared byreacting a composition conforming to the following:

wherein;

R is alkyl having 8 to 22 carbon atoms;

and

wherein;

R is alkyl having 8 to 22 carbon atoms;

and

(c) a sorbitan ester conforming to the following structure:

R¹ is alkyl having from 7 to 21 carbon atoms;with a polymerizing agent conforming to the following structure

-   -   Cl—CH₂CH(OH)CH₂Cl        and        optionally a functionalizing agent selected from the group        consisting of:

Cl—CH₂—CH(OH)—SO₃M;Cl—CH₂—CH(OH)CH₂—SO₄M;Cl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂;and mixtures thereof;wherein:R¹ is CH₃—(CH₂)_(n)—n is an integer ranging from 6 to 36;M is needed for charge balance and is selected from the group consistingof

-   -   H, Na, K, or NH₄.

Preferred Embodiment

In a preferred embodiment the functionalizing agent is:

R¹ is CH₃—(CH₂)_(n)—n is an integer ranging from 6 to 36.

In a preferred embodiment n is 11.

In a preferred embodiment n is 13.

In a preferred embodiment n is 15.

In a preferred embodiment n is 17.

In a preferred embodiment n is 19.

In a preferred embodiment n is 35.

In another preferred embodiment the functionalizing agent is

-   -   Cl—CH₂—CH(OH)—SO₃M        M is needed for charge balance and is selected from the group        consisting of    -   H, Na, K, or NH₄.

In another preferred embodiment the functionalizing agent is

-   -   Cl—CH₂—CH(OH)CH₂—SO₄M        M is needed for charge balance and is selected from the group        consisting of    -   H, Na, K, or NH₄.

In another preferred embodiment the functionalizing agent is

-   -   Cl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂        M is needed for charge balance and is selected from the group        consisting of    -   H, Na, K, or NH₄.

In a preferred embodiment the functionalizing agent is a mixture of;

Cl—CH₂—CH(OH)—SO₃M;Cl—CH₂—CH(OH)CH₂—SO₄M;andCl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂;wherein:R¹ is CH₃—(CH₂)_(n)—n is an integer ranging from 5 to 35;M is needed for charge balance and is selected from the group consistingof

-   -   H, Na, K, or NH₄.

In a preferred embodiment the effective conditioning concentrationranges from 0.1 to 25% by weight.

In a preferred embodiment the effective conditioning concentrationranges from 1% to 15% by weight.

EXAMPLES Preparation of Alkyl Glycosides

Alkyl Glycosides are raw materials used to make the surface-activepolyglycoside derivatives of the present invention.

Saccharides useful in the process of making alkyl glycosides aresaccharides that can be alkylated in the “1” position, commonly referredto as “reducing saccharides”, or higher saccharides that can behydrolyzed to provide such a saccharide. These saccharides are typicallycomprised of aldo- or keto-hexoses or pentoses.

Examples of saccharides include glucose (dextrose), fructose, mannose,galactose, talose, allose, altrose, idose, arabinose, xylose, lyxose,and ribose. Examples of hydrolyzable saccharides that are a source ofreducing saccharides include starch, maltose, sucrose, lactose,maltotriose, xylobiose, mellibiose, cellobiose, raffinose, stachiose,methyl glycosides, butyl glycosides, levoglucosan, and1,6-anhydroglucofuranose.

The physical form of the saccharide may vary. The saccharide willtypically be in a fluid (as opposed to a solid) state, e.g. as a melt oran aqueous syrup, during at least a portion of the period of reaction,if not for a predominant portion of the period of the reaction.Crystalline (e.g. anhydrous or hydrates) or amorphous saccharide solidsin various particle sizes, e.g. granules, powders, etc., can be used,but the heating of the reaction medium may well fluidize at least aportion of a solid reactant, if not a predominant portion of thesaccharide reactant. Aqueous syrups of saccharides, typically atsaccharide solids of between about 10% and 90% dry solids by weight canalso be used. Indeed, the use of the hydrophobic catalysts of thisinvention should show the most improved results over conventionalcatalysts in the context of the use of aqueous syrup reactants ascompared with processes which employ solid saccharide reactants,particularly with respect to avoiding the formation of deleteriousamounts of polysaccharides and very high DP alkyl glycosides during theglycoside formation reaction.

The preferred saccharides are glucose, galactose, xylose and arabinose,or mixtures thereof, for reasons of availability, low cost, andconvenience. Glucose in the anhydrous crystalline form is preferred,although dextrose monohydrate, corn syrups of high dry solids (typically50% to 80% dry solids) and a high dextrose equivalence (D.E.) (typicallygreater than 90 D.E and most commonly 95 D.E.) can be commonly employed.Indeed, while the higher the purity of the dextrose source, the betterthe quality of the product (other things being equal), the catalysts ofthis invention allow the use of a lower purity dextrose source and yetyield a product of substantially equivalent quality as compared withprior catalysts. Because of the ready availability of glucose and itsoligomers, much of the remaining description is particularly suited tothe use of glucose in its various forms.

Alcohols useful in the process of this invention are hydroxyl-functionalorganic compounds capable of alkylating a saccharide in the “1”position. The alcohol can be naturally occurring, synthetic, or derivedfrom natural sources and/or derivatized. Examples include monohydricalcohols (more fully discussed below) and polyhydric alcohols (e.g.ethylene glycol, propylene glycol, polyethylene glycols, polypropyleneglycols, butylene glycol, glycerol, trimethylolpropane, pentaerythritol,polyester polyols, polyisocyanate polyols, and so on). Other examplesinclude aromatic alcohols such as benzyl alcohol, phenol, substitutedphenols (e.g. alkylphenols) and alkoxylates of each.

Preferred alcohols are monohydric alcohols containing from about 1 toabout 30 carbon atoms. They may be primary or secondary alcohols,straight or branched chain, saturated or unsaturated (e.g. allylalcohol, 2-ethylhexenyl alcohol and oleyl alcohol) alkyl or aralkylalcohols, ether alcohols, cyclic alcohols, or heterocyclic alcohols. Ingeneral, these alcohols have minimal solvent power for the saccharidemolecule. Examples of the monohydric alcohols which may be employed inthe present invention include methyl alcohol, isopropyl alcohol, butylalcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol,tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecylalcohol, pentacosyl alcohol, oleyl alcohol, linoleyl alcohol, isoborneolalcohol, hydroabietyl alcohol, phenoxyethanol, phenoxypolyethoxyethanolcontaining five ethoxy groups, 2-methyl-7-ethyl-4-undecanol, andmixtures of one or more of the above.

A preferred group of alcohols are alkanols having the formula ROHwherein R represents an alkyl group having from 8 to 30 carbon atoms. Aparticularly preferred group of alcohols are those wherein R representsan alkyl radical having from 8 to 20, preferably 11 to 18, carbon atoms.The alkyls can be straight or branched chain.

Alkyl Glycoside Examples Example 1

A one-liter, four-necked, round-bottomed flask was equipped through itscenter neck with an overhead mechanical stirrer, through a second neckwith a distillation head fitted with an addition funnel and acondenser/receiver/vacuum take-off assembly, through a third neck fittedwith a three hole rubber stopper with a capillary nitrogen bleed, acalibrated mercury thermometer and a vacuum tight temperature controllerprobe, and on the fourth neck with a septum for sampling.

The flask was charged with 602.4 g (3.105 moles) of a commercial mixtureof C₁₁ to C₁₅ (98% C₁₂ and C₁₃) straight and branched alkanols (Neodol23 available form Shell Chemical Co.) and 136.6 g (0.69 moles) of acommercially available dextrose monohydrate (Staleydex 333, availablefrom A. E. Staley Mfg. Co. at 9.0% moisture). The slurry was heated at avacuum of 30 mm Hg (absolute). Water was released starting at about57.degree. C. and heating was continued until the slurry had reached110.degree. C. At this time 3.2 g (0.00345 mole of a commerciallyavailable mixture of 50% dinonylnaphthalenesulfonic acid in heptane(available from King Industries) was added as a catalyst and thetheoretical volume of water distilled at about a linear rate over 8hours. After stirring an additional hour, a stoichiometric amount ofaqueous NaOH (33% in H₂O) was added. An aliquot of the neutralizedreaction mixture (3.39 g, 1 g dissolved substance) was dissolved in atotal volume of 10 ml with 1:1 isopropanol:water. The pH of thissolution was 7.8.

The remainder of the reaction mixture was evaporated to a clear melt at200.degree. C. and 1 mm pressure using a Leybold-Heraeus Distact™ wipedfilm evaporator operating at a feed rate of 700 ml/hr.

The residue was analyzed using a combination of gas and liquidchromatographic techniques as well as NMR spectroscopy and was shown tocontain less than 0.2% free alcohol and less than 2% polar species(HPLC) and an NMR mole ratio of glucose rings to fatty chains of about1.4.

Example 2-9

The same one-liter, four-necked, round-bottomed flask was equippedthrough its center neck with an overhead mechanical stirrer, through asecond neck with a distillation head fitted with an addition funnel anda condenser/receiver/vacuum take-off assembly, through a third neckfitted with a three hole rubber stopper with a capillary nitrogen bleed,a calibrated mercury thermometer and a vacuum tight temperaturecontroller probe, and on the fourth neck with a septum for sampling.

The flask was charged with 3.105 moles of the specified alcohol and136.6 g (0.69 moles) of a commercially available dextrose monohydrate(Staleydex 333, available from A. E. Staley Mfg. Co. at 9.0% moisture).The slurry was heated at a vacuum of 30 mm Hg (absolute). Water wasreleased starting at about 57.degree. C. and heating was continued untilthe slurry had reached 110.degree. C. At this time 3.2 g (0.00345 moleof a commercially available mixture of 50% dinonylnaphthalenesulfonicacid in heptane (available from King Industries) was added as a catalystand the theoretical volume of water distilled at about a linear rateover 8 hours. After stirring an additional hour, a stoichiometric amountof aqueous NaOH (33% in H₂O) was added. An aliquot of the neutralizedreaction mixture (3.39 g, 1 g dissolved substance) was dissolved in atotal volume of 10 ml with 1:1 isopropanol:water. The pH of thissolution was 7.8.

The remainder of the reaction mixture was evaporated to a clear melt at200.degree. C. and 1 mm pressure using a Leybold-Heraeus Distact™ wipedfilm evaporator operating at a feed rate of 700 ml/hr.

The residue was analyzed using a combination of gas and liquidchromatographic techniques as well as NMR spectroscopy and was shown tocontain less than 0.2% free alcohol and less than 2% polar species(HPLC) and an NMR mole ratio of glucose rings to fatty chains of about1.4. The hydroxyl value was run on the resultant product and isindicated below.

Example Alkyl OH Value 2 C₁₂H₂₅ 691.9 3 C₁₀H₂₁ 741.8 4 C₈H₁₇ 795.4 5C₁₄H₂₇ 653.8 6 C₁₈H₃₇ 584.4 7 C₁₈H₃₅ 586.7 8 C₂₀H₄₂ 555.1 9 C₂₂H₄₂ 531.2

Sorbitan Esters of Fatty Acids (Sorbitan Ester)

Sorbitan esters of fatty acid is called sorbitan ester, which isproduced by esterification of sorbitol and fatty acid. It is a mixtureof sorbitol ester and sorbide ester, which are simultaneously producedas well as sorbitan ester. There are many types of sorbitan esters withdifferent kinds of fatty acids and various degrees of esterification.

Commercially available materials come from a variety of suppliersincluding Croda. The following is taken from their catalogue:

Viscosity Color and at 25° C. form or pour Product Chemical compositionHLB at 25° C.¹ point₂ Span 20 Sorbitan monolaurate 8.6 Amber liquid 4250cs Span 40 Sorbitan monopalmitate 6.7 Tan solid 48° C. Span 60³ Sorbitanmonostearate 4.7 Tan solid 53° C. Span 60K Sorbitan monostearate 4.7 Tansold 53° C. (Kosher grade) Span 65 Sorbitan tristearate 2.1 Cream solid53° C. Span 80 Sorbitan monooleate 4.3 Amber liquid 1000 cs Span 85Sorbitan trioleate 1.8 Amber liquid  210 cs

The above products are listed as examples of products but the productsused in the preparation of the compounds of the present invention wereverified by wet analysis and proton and C13 nm r so they are independentof trade names.

Sorbitan ester useful as raw materials for the preparation of thecompounds of the present invention conform to the following structure:

R¹ is alkyl having from 7 to 21 carbon atoms;

Examples 10-16

Example R¹ 10 7 11 9 12 11 13 13 14 15 15 17 16 21

Alkyl Polyglycosides Functionaized Products

There are a number of groups that can be introduced into the finishedalkyl polyglycoside/sorbitol ester copolymer. These include phosphates;sulfates, alkoxylate and quaternary groups.

It will be clearly understood that the alkyl polyglycoside/sorbitanester copolymer of the present invention have a number of hydroxylgroups present in the molecule. The number of hydroxyl groupsfunctionalized will have a profound effect upon the degree of increasedwater solubility of the molecule.

The present invention includes a functionalization of a low number ofhydroxyl groups (one per molecule) to a high number (all groups on themolecule). The preferred number to functionalize is an intermediatenumber of groups (approximately half of the number present).

Example 17 1,3 Dichloro Isopropanol

The polymerizing agent of the present invention is;

-   -   Cl—CH₂CH(OH)CH₂Cl (1,3 dichloro isopropanol)

1,3 dichloro isopropanol is an item of commerce commercially availablefrom Dixie Chemical.

Example 18 Chloro Hydroxypropyl Sulfonate

The product conforms to the following structure:

-   -   Cl—CH₂—CH(OH)CH₂—SO₃Na.        It is an item of commerce available from Siltech Corporation in        Toronto Canada.

Example 19 Chloro Hydroxypropyl Sulfate

The product conforms to the following structure:

-   -   Cl—CH₂—CH(OH)CH₂—SO₄K.        It is an item of commerce available from Siltech Corporation in        Toronto Canada.

Example 20 Chloro Hydroxypropyl Phosphate

The product conforms to the following structure:

-   -   Cl—CH₂—CH(OH)CH₂—O—P(O)O Na.        It is an item of commerce available from Siltech Corporation in        Toronto Canada.        Chloro Hydroxypropyl Quat        The product conforms to the following structure:

It is an item of commerce available from Siltech Corporation in TorontoCanada.

Example n Value 21 5 22 11 23 15 24 17 25 21 26 35

General Procedure—To a flask equipped with agitation, heat, thermometerand nitrogen sparge is added the specified amount of the specified alkylpolyglycoside (example 1-9), the specified amount of the specifiedsorbitan ester (example 10-16) and enough water to make the finalproduct have a solids of 35% by weight. Next, the specified amount of1,3 dichloro isopropanol is (Example 17) added under good agitation andnitrogen sparge. Next is added 0.5% sodium methylate. Next add thespecified number of grams of the specified functionalizing agent(Examples 18-26). The % is by weight and is based upon the total amountof all materials reacted. Nitrogen sparge is simply nitrogen bubbledthrough the liquid contents of the flask. This keeps the color light,minimizing oxidation and color formation. The reaction mass is heated to90-100° C., and is held for 5-8 hours. The reaction progress ismonitored by formation of chloride ion. Once the theoretical value isreached, the reaction is terminated and the product is used withoutadditional purification.

Example 27-37

APG Sorb Ester Ex 17 Functionalizing Agent Example Ex Grams Ex GramsGrams Example Grams 27 1 246.0 10 200.0 65.0 18 130.0 28 2 116.0 11300.0 65.0 19 150.0 29 3 288.0 12 100.0 65.0 20 150.0 30 4 322.0 13150.0 65.0 21 130.0 31 5 328.0 14 200.0 65.0 22 130.0 32 6 400.0 15126.0 65.0 23  65.0 33 1 300.0 16 146.0 198.0 24 130.0 34 2 216.0 15200.0 198.0 25 150.0 35 3 288.0 14 100.0 198.0 26 200.0 36 4 300.0 13175.0 132.0 18 180.0 37 5 328.0 12 200.0 330.0 19 160.0

The compounds of the invention range from clear yellow liquids topastes. They are outstanding emulsifiers for making water in oil and oilin water emulsions.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthhereinabove but rather that the claims be construed as encompassing allthe features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those skilled in the art to which the invention pertains.

1. A composition prepared by reacting:

wherein; R is alkyl having 8 to 22 carbon atoms; and

wherein; R is alkyl having 8 to 22 carbon atoms; (c) a sorbitan esterconforming to the following structure:

R¹ is alkyl having from 7 to 21 carbon atoms; with a polymerizing agentconforming to the following structure Cl—CH₂CH(OH)CH₂Cl in water: andoptionally a functionalizing agent selected from the group consistingof:

and mixtures thereof; wherein: R¹ is CH₃—(CH₂)_(n)— n is an integerranging from 6 to 36; M is needed for charge balance and is selectedfrom the group consisting of H, Na, K, or NH₄.
 2. A composition of claim1 wherein n is
 13. 3. A composition of claim 1 wherein n is
 15. 4. Acomposition of claim 1 wherein n is
 17. 5. A composition of claim 1wherein n is
 19. 6. A composition of claim 1 wherein n is
 35. 7. Acomposition of claim 1 wherein the functionalizing agent isCl—CH₂—CH(OH)—SO₃M M is needed for charge balance and is selected fromthe group consisting of H, Na, K, or NH₄.
 8. A composition of claim 1wherein the functionalizing agent is Cl—CH₂—CH(OH)CH₂—SO₄M M is neededfor charge balance and is selected from the group consisting of H, Na,K, or NH₄.
 9. A composition of claim 1 wherein the functionalizing agentis Cl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂ M is needed for charge balance and isselected from the group consisting of H, Na, K, or NH₄.
 10. Acomposition of claim 1 wherein the functionalizing agent is a mixtureof;

Cl—CH₂—CH(OH)—SO₃M; Cl—CH₂—CH(OH)CH₂—SO₄M; andCl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂; wherein: R¹ is CH₃—(CH₂)_(n)— n is aninteger ranging from 5 to 35; M is needed for charge balance and isselected from the group consisting of H, Na, K, or NH₄.
 11. A processfor conditioning hair or skin which comprises contacting the hair orskin with an effective conditioning concentration of a compositionprepared by reacting:

wherein; R is alkyl having 8 to 22 carbon atoms; and

wherein; R is alkyl having 8 to 22 carbon atoms; (c) a sorbitan esterconforming to the following structure:

R¹ is alkyl having from 7 to 21 carbon atoms; with a polymerizing agentconforming to the following structure Cl—CH₂CH(OH)CH₂Cl in water: andoptionally a functionalizing agent selected from the group consistingof:

and mixtures thereof; wherein: R¹ is CH₃—(CH₂)_(n)— n is an integerranging from 6 to 36; M is needed for charge balance and is selectedfrom the group consisting of H, Na, K, or NH₄.
 12. A process of claim 11wherein the effective conditioning concentration ranges from 0.1 to 25%by weight.
 13. A process of claim 11 wherein the effective conditioningconcentration ranges from 1% to 15% by weight.
 14. A process of claim 12wherein the functionalizing agent is:

R¹ is CH₃—(CH₂)_(n)— n is an integer ranging from 6 to
 36. 15. A processof claim 12 wherein the functionalizing agent is Cl—CH₂—CH(OH)—SO₃M M isneeded for charge balance and is selected from the group consisting ofH, Na, K, or NH₄.
 16. A process of claim 12 wherein the functionalizingagent is Cl—CH₂—CH(OH)CH₂—SO₄M M is needed for charge balance and isselected from the group consisting of H, Na, K, or NH₄.
 17. A process ofclaim 12 wherein the functionalizing agent isCl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂ M is needed for charge balance and isselected from the group consisting of H, Na, K, or NH₄.
 18. A process ofclaim 12 wherein the functionalizing agent is a mixture of;

and Cl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂; wherein: R¹ is CH₃—(CH₂)_(n)— n is aninteger ranging from 5 to 35; M is needed for charge balance and isselected from the group consisting of H, Na, K, or NH₄.
 19. A process ofclaim 13 wherein the functionalizing agent is a mixture of;

Cl—CH₂—CH(OH)—SO₃M; Cl—CH₂—CH(OH)CH₂—SO₄M; andCl—CH₂—CH(OH)—CH₂—OP(O)—(OM)₂; wherein: R¹ is CH₃—(CH₂)_(n)— n is aninteger ranging from 5 to 35; M is needed for charge balance and isselected from the group consisting of H, Na, K, or NH₄.